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1.
Angew Chem Int Ed Engl ; 59(10): 4043-4050, 2020 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-31919948

RESUMO

Ni,N-doped carbon catalysts have shown promising catalytic performance for CO2 electroreduction (CO2 R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni-N bonding and correlating CO2 reduction (CO2 R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO2 R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal-porphyrin catalysts.

3.
Angew Chem Int Ed Engl ; 57(39): 12840-12844, 2018 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-30112793

RESUMO

Iron cations are essential for the high activity of nickel and cobalt-based (oxy)hydroxides for the oxygen evolution reaction, but the role of iron in the catalytic mechanism remains under active investigation. Operando X-ray absorption spectroscopy and density functional theory calculations are used to demonstrate partial Fe oxidation and a shortening of the Fe-O bond length during oxygen evolution on Co(Fe)Ox Hy . Cobalt oxidation during oxygen evolution is only observed in the absence of iron. These results demonstrate a different mechanism for water oxidation in the presence and absence of iron and support the hypothesis that oxidized iron species are involved in water-oxidation catalysis on Co(Fe)Ox Hy .

4.
Nano Lett ; 17(11): 6922-6926, 2017 11 08.
Artigo em Inglês | MEDLINE | ID: mdl-28991484

RESUMO

Nickel (oxy)hydroxide-based (NiOxHy) materials are widely used for energy storage and conversion devices. Understanding dynamic processes at the solid-liquid interface of nickel (oxy)hydroxide is important to improve reaction kinetics and efficiencies. In this study, in situ electrochemical atomic force microscopy (EC-AFM) was used to directly investigate dynamic changes of single-layered Ni(OH)2 nanosheets during electrochemistry measurements. Reconstruction of Ni(OH)2 nanosheets, along with insertion of ions from the electrolyte, results in an increase of the volume by 56% and redox capacity by 300%. We also directly observe Fe cations adsorb and integrate heterogeneously into or onto the nanosheets as a function of applied potential, further increasing apparent volume. Our findings are important for the fundamental understanding of NiOxHy-based supercapacitors and oxygen-evolution catalysts, illustrating the dynamic nature of Ni-based nanostructures under electrochemical conditions.

5.
J Am Chem Soc ; 139(33): 11361-11364, 2017 08 23.
Artigo em Inglês | MEDLINE | ID: mdl-28789520

RESUMO

Fe is a critical component of record-activity Ni/Fe (oxy)hydroxide (Ni(Fe)OxHy) oxygen evolution reaction (OER) catalysts, yet its precise role remains unclear. We report evidence for different types of Fe species within Ni(Fe)OxHy- those that are rapidly incorporated into the Ni oxyhydroxide from Fe cations in solution (and that are likely at edges or defects) and are responsible for the enhanced OER activity, and those substituting for bulk Ni that modulate the observed Ni voltammetry. These results suggest that the exceptional OER activity of Ni(Fe)OxHy does not depend on Fe in the bulk or on average electrochemical properties of the Ni cations measured by voltammetry, and instead emphasize the role of the local structure.

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